US20080181809A1 - Titanium-Based Alloy - Google Patents

Titanium-Based Alloy Download PDF

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Publication number
US20080181809A1
US20080181809A1 US11/630,428 US63042805A US2008181809A1 US 20080181809 A1 US20080181809 A1 US 20080181809A1 US 63042805 A US63042805 A US 63042805A US 2008181809 A1 US2008181809 A1 US 2008181809A1
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United States
Prior art keywords
alloy
titanium
molybdenum
vanadium
aluminum
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Abandoned
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US11/630,428
Inventor
Tetyukhin Vladislav
Levin Igor
Trubochkin Alexandr
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VSMPO Avisma Corp PSC
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VSMPO Avisma Corp PSC
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Application filed by VSMPO Avisma Corp PSC filed Critical VSMPO Avisma Corp PSC
Publication of US20080181809A1 publication Critical patent/US20080181809A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

Definitions

  • the invention relates to the field of metallurgy and particularly to the field of developing state-of-the-art titanium alloys used for making high-strength and high-workability articles including large articles, i.e., alloys of high versatility.
  • Titanium alloys are widely used as aerospace materials, e.g., in air-planes and rockets, since the alloys are mechanically tough and are comparatively light.
  • Ti6Al4V The most widely used titanium alloy is Ti6Al4V (B. A. Kalachyov, I. S. Polkin and V. D. Talalayev. Titanium Alloys of Different countries. Reference Book. Moscow: VILS, 2000, p. 58-59-[1]).
  • This alloy was developed in the USA during the 1950s. It is characterized by medium strength of 850 up to 1000 MPa and high workability. It is a good material to work by forming: forging, die forging, and extruding. It is widely used in aeronautical and aerospace engineering, shipbuilding, the automotive industry, etc., as well as in manufacturing fasteners for various applications. This alloy is good for working by all types of welding including diffusion bonding.
  • Ti6Al4V is its insufficient versatility. It is difficult to make rolled sheet products, foil, and tubes thereof since the alloy possesses relatively high resistance to deformation, which, at deformation temperatures below 800° C., leads to the generation of defects such as cracks and shortens the life of working tools, or necessitates costly tools.
  • Pseudo- ⁇ -titanium alloy Grade 9 (Ti-3AI-2.5V) is highly cold-workable (see [1], p. 44, 45). The strength of this alloy is intermediate between that of Ti-6AI-4V and that of titanium (600-800 MPa). This alloy is used cold-worked and stress-annealed; it is characterized by high corrosion resistance in various media including sea water. This alloy is used in making tubes for hydraulics and fuel systems of airplanes, rockets, and submarines.
  • the closest analog of the invented alloy is an ⁇ + ⁇ -titanium alloy consisting of 3.0-5.0 Al; 2.1-3.7 V; 0.85-3.15 Mo; 0.85-3.15 Fe; 0.06-0.2 O 2 , and inevitable impurities (prior art Japanese application No. 3007214 B2, filed Feb. 7, 2000).
  • an optimum mix of ⁇ - and ⁇ -stabilizing alloying elements is provided in a semi-finished product.
  • the invention provides a titanium-based alloy consisting of aluminum, vanadium, molybdenum, iron, and oxygen in the following weight percent ratio:
  • the combination of high strength and ductility in the invented alloy is achieved through targeted selection and experimental evaluation of the alloying ranges.
  • the content of ⁇ -stabilizers (aluminum, oxygen) and ⁇ -stabilizers (vanadium, molybdenum, and iron) was determined so as to meet the objective.
  • Aluminum is an ⁇ -stabilizer for the ⁇ + ⁇ -titanium alloys, which contributes to increased mechanical strength. However, if the aluminum content is below 3.5%, strength sufficient to meet the invention goal cannot be obtained; whereas if the aluminum content exceeds 4.4%, resistance to hot deformation is increased and ductility at lower temperatures is decreased, which leads to lower productivity.
  • Vanadium is added to titanium as a ⁇ -stabilizer for the ⁇ + ⁇ -titanium alloys, increasing mechanical strength without forming brittle intermetallic compounds with titanium.
  • the presence of vanadium in the alloy impedes formation of ⁇ 2 -superstructure in the ⁇ -phase as the ⁇ -phase stabilizes, and increases both strength and ductility. If the vanadium content is below 2%, strength sufficient to meet the invention goal cannot be obtained; whereas if the vanadium content exceeds 4.0%, the superplastic elongation is decreased by lowering of the beta transus. Vanadium content within the range of 2.0-4.0% in this alloy has the benefit that scrap of the most-used Ti6Al4V can be utilized.
  • Molybdenum is added to titanium as a ⁇ -stabilizer for the ⁇ + ⁇ -titanium alloys. If molybdenum is added within the range of 0.1-0.8%, it can fully dissolve in the ⁇ -phase, so that sufficient strength is obtained without deteriorating plastic properties. If the molybdenum content exceeds 0.8%, it increases the specific weight of the alloy due to the fact that molybdenum is a heavy metal, and the plastic properties of the alloy deteriorate. If the molybdenum content is below 0.1%, molybdenum does not fully contribute to the alloy's properties.
  • Iron added to the alloy up to 0.4% increases the volume ratio of the ⁇ -phase, decreasing resistance to deformation in hot working of this alloy, thus evading the generation of such defects as cracking.
  • An iron content exceeding 0.4% generates a segregation phase with beta-flecks upon melting and solidifying the alloy, which leads to heterogeneity of mechanical properties, especially ductility.
  • Oxygen enhances mechanical strength by constituting a solid solution, mainly in the ⁇ -phase. If the oxygen content exceeds 0.25%, the alloy ductility may deteriorate.
  • the alloy may contain up to 0.1% of carbon and up to 0.05% of nitrogen as inevitable impurities; the total quantity of impurities shall not exceed 0.16%.
  • a bar of 50-mm diameter was made of each ingot by hot working. Part of the bars were heat treated by annealing at 750° C., soaking for 1 hour and cooling in the air. The mechanical properties at room temperature were evaluated for the bars heat treated and for those not heat treated. The evaluation results are given in Table 2. In addition, the mechanical properties of upset ⁇ -phase workpieces, which were heat treated at 710° C., soaked for 3 hours and cooled in air, were evaluated. The results of mechanical testing of upset ⁇ + ⁇ and ⁇ -field workpieces are given in Table 2.
  • the invented alloy is highly versatile, economically beneficial and has lower cost due to the fact that scrap of widely known alloys, such as Ti6Al4V, can be used for its production.
  • This alloy possesses required and sufficient mechanical properties and can be utilized for making a wide range of products, such as large forgings and die forgings, thin sheets and foil, by working in both the ⁇ + ⁇ -field and the ⁇ -field.

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Forging (AREA)
  • Materials For Medical Uses (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The titanium-based alloy consists of aluminum, vanadium, molybdenum, iron, and oxygen in the following weight percent ratio: aluminum 3.5-4.4, vanadium 2.0-4.0, molybdenum 0.1-0.8, iron maximum 0.4, oxygen maximum 0.25, the balance titanium. The technical objective is to provide a versatile alloy to be used for making large forgings and die forgings, rolled sheet products and foil having sufficient strength, ductility and structure.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The invention relates to the field of metallurgy and particularly to the field of developing state-of-the-art titanium alloys used for making high-strength and high-workability articles including large articles, i.e., alloys of high versatility.
  • Titanium alloys are widely used as aerospace materials, e.g., in air-planes and rockets, since the alloys are mechanically tough and are comparatively light.
  • 2. Background Information
  • The most widely used titanium alloy is Ti6Al4V (B. A. Kalachyov, I. S. Polkin and V. D. Talalayev. Titanium Alloys of Different Countries. Reference Book. Moscow: VILS, 2000, p. 58-59-[1]). This alloy was developed in the USA during the 1950s. It is characterized by medium strength of 850 up to 1000 MPa and high workability. It is a good material to work by forming: forging, die forging, and extruding. It is widely used in aeronautical and aerospace engineering, shipbuilding, the automotive industry, etc., as well as in manufacturing fasteners for various applications. This alloy is good for working by all types of welding including diffusion bonding.
  • The disadvantage of Ti6Al4V is its insufficient versatility. It is difficult to make rolled sheet products, foil, and tubes thereof since the alloy possesses relatively high resistance to deformation, which, at deformation temperatures below 800° C., leads to the generation of defects such as cracks and shortens the life of working tools, or necessitates costly tools.
  • Pseudo-α-titanium alloy Grade 9 (Ti-3AI-2.5V) is highly cold-workable (see [1], p. 44, 45). The strength of this alloy is intermediate between that of Ti-6AI-4V and that of titanium (600-800 MPa). This alloy is used cold-worked and stress-annealed; it is characterized by high corrosion resistance in various media including sea water. This alloy is used in making tubes for hydraulics and fuel systems of airplanes, rockets, and submarines.
  • The disadvantage of this alloy also is its low versatility since it requires stress relieving in making large structural parts thereof. Therefore, such articles have to be annealed which reduces the strength of the Grade 9 alloy down to 400-500 MPa.
  • The closest analog of the invented alloy is an α+β-titanium alloy consisting of 3.0-5.0 Al; 2.1-3.7 V; 0.85-3.15 Mo; 0.85-3.15 Fe; 0.06-0.2 O2, and inevitable impurities (prior art Japanese application No. 3007214 B2, filed Feb. 7, 2000).
  • The disadvantage of this alloy is that it is rich in Fe and Mo and, therefore, is prone to segregation. In order to reduce the possibility of segregational heterogeneity a special ingot melting technology must be used, followed by rolling and forging at a small deformation rate in order to exclude decoration by “beta-flecks”, which processing decreases productivity.
    • OBJECT OF THE INVENTION
  • It is an object of the invention to provide a versatile titanium alloy having minimal manufacturing costs and capable of being made into a wide variety of products, such as large forgings and die forgings, as well as rolled sheet products and foil having sufficient strength, plastic properties and structure.
    • SUMMARY OF THE INVENTION
  • According to the invention an optimum mix of α- and β-stabilizing alloying elements is provided in a semi-finished product.
  • The invention provides a titanium-based alloy consisting of aluminum, vanadium, molybdenum, iron, and oxygen in the following weight percent ratio:
  • wt. %
    aluminum 3.5-4.4
    vanadium 2.0-4.0
    molybdenum 0.1-0.8
    iron max 0.4 
    oxygen max 0.25
    titanium balance
  • The combination of high strength and ductility in the invented alloy is achieved through targeted selection and experimental evaluation of the alloying ranges. The content of α-stabilizers (aluminum, oxygen) and β-stabilizers (vanadium, molybdenum, and iron) was determined so as to meet the objective.
  • Aluminum is an α-stabilizer for the α+β-titanium alloys, which contributes to increased mechanical strength. However, if the aluminum content is below 3.5%, strength sufficient to meet the invention goal cannot be obtained; whereas if the aluminum content exceeds 4.4%, resistance to hot deformation is increased and ductility at lower temperatures is decreased, which leads to lower productivity.
  • Vanadium is added to titanium as a β-stabilizer for the α+β-titanium alloys, increasing mechanical strength without forming brittle intermetallic compounds with titanium. The presence of vanadium in the alloy impedes formation of α2-superstructure in the α-phase as the β-phase stabilizes, and increases both strength and ductility. If the vanadium content is below 2%, strength sufficient to meet the invention goal cannot be obtained; whereas if the vanadium content exceeds 4.0%, the superplastic elongation is decreased by lowering of the beta transus. Vanadium content within the range of 2.0-4.0% in this alloy has the benefit that scrap of the most-used Ti6Al4V can be utilized.
  • Molybdenum is added to titanium as a β-stabilizer for the α+β-titanium alloys. If molybdenum is added within the range of 0.1-0.8%, it can fully dissolve in the α-phase, so that sufficient strength is obtained without deteriorating plastic properties. If the molybdenum content exceeds 0.8%, it increases the specific weight of the alloy due to the fact that molybdenum is a heavy metal, and the plastic properties of the alloy deteriorate. If the molybdenum content is below 0.1%, molybdenum does not fully contribute to the alloy's properties.
  • Iron added to the alloy up to 0.4% increases the volume ratio of the β-phase, decreasing resistance to deformation in hot working of this alloy, thus evading the generation of such defects as cracking. An iron content exceeding 0.4% generates a segregation phase with beta-flecks upon melting and solidifying the alloy, which leads to heterogeneity of mechanical properties, especially ductility.
  • Oxygen enhances mechanical strength by constituting a solid solution, mainly in the α-phase. If the oxygen content exceeds 0.25%, the alloy ductility may deteriorate.
  • The alloy may contain up to 0.1% of carbon and up to 0.05% of nitrogen as inevitable impurities; the total quantity of impurities shall not exceed 0.16%.
    • DETAILED DESCRIPTION OF AN ILLUSTRATIVE EMBODIMENT
  • To evaluate the properties of the claimed alloy ingots were melted by the method of double vacuum-arc remelt, having the following chemical compositions (Table 1).
  • TABLE 1
    Chemical Composition, wt. %
    Alloy Al V Mo Fe O
    1 3.9 2.2 0.2 0.13 0.17
    2 4.3 2.8 0.3 0.24 0.23
    3 4.3 3.3 0.6 0.32 0.20
  • TABLE 2
    Mechanical Properties
    σ?, σ0.2,
    Alloy Heat Treatment MPa MPa δ, % ψ, %
    1 W/o annealing 810 735 15.2 38.2
    750° C. 1 hour, air 780 693 13.2 32.0
    2 W/o annealing 960 840 14.2 33.1
    750° C. 1 hour, air 920 845 13.6 32.5
    3 α + β 710° C. 3 hours, 900 835 15 33.0
    air
    β 710° C. 3 hours, 870 800 14 28.0
    air
  • A bar of 50-mm diameter was made of each ingot by hot working. Part of the bars were heat treated by annealing at 750° C., soaking for 1 hour and cooling in the air. The mechanical properties at room temperature were evaluated for the bars heat treated and for those not heat treated. The evaluation results are given in Table 2. In addition, the mechanical properties of upset β-phase workpieces, which were heat treated at 710° C., soaked for 3 hours and cooled in air, were evaluated. The results of mechanical testing of upset α+β and β-field workpieces are given in Table 2.
  • In comparison with known alloys the invented alloy is highly versatile, economically beneficial and has lower cost due to the fact that scrap of widely known alloys, such as Ti6Al4V, can be used for its production. This alloy possesses required and sufficient mechanical properties and can be utilized for making a wide range of products, such as large forgings and die forgings, thin sheets and foil, by working in both the α+β-field and the β-field.

Claims (1)

1. A titanium-based alloy substantially consisting of aluminum at 3.5 to 4.4 wt. %, vanadium at 2.0 to 4.0 wt. %, molybdenum at 0.1 to 0.8 wt. %, iron at a maximum of 0.4 wt. %, oxygen at a maximum of 0.25 wt. % and a balance of titanium and inevitable impurities.
US11/630,428 2004-07-30 2005-07-14 Titanium-Based Alloy Abandoned US20080181809A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
RU2004123500 2004-07-30
RU2004123500/02A RU2269584C1 (en) 2004-07-30 2004-07-30 Titanium-base alloy
PCT/RU2005/000381 WO2006014124A1 (en) 2004-07-30 2005-07-14 Titanium-based alloy

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US (1) US20080181809A1 (en)
EP (1) EP1783235B1 (en)
AT (1) ATE420217T1 (en)
DE (1) DE602005012284D1 (en)
DK (1) DK1783235T3 (en)
ES (1) ES2320684T3 (en)
RU (1) RU2269584C1 (en)
WO (1) WO2006014124A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080199350A1 (en) * 2001-11-22 2008-08-21 Tetyukhin Vladislav Valentinov Metastable beta-titanium alloy
US20160008903A1 (en) * 2014-07-10 2016-01-14 The Boeing Company Titanium Alloy for Fastener Applications
US9631261B2 (en) 2010-08-05 2017-04-25 Titanium Metals Corporation Low-cost alpha-beta titanium alloy with good ballistic and mechanical properties

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US20040221929A1 (en) 2003-05-09 2004-11-11 Hebda John J. Processing of titanium-aluminum-vanadium alloys and products made thereby
US7837812B2 (en) 2004-05-21 2010-11-23 Ati Properties, Inc. Metastable beta-titanium alloys and methods of processing the same by direct aging
CN101543948B (en) * 2008-03-28 2011-06-08 北京有色金属研究总院 Processing technology of Ti5Mo5V2Cr3Al alloy
DE102009050603B3 (en) * 2009-10-24 2011-04-14 Gfe Metalle Und Materialien Gmbh Process for producing a β-γ-TiAl base alloy
RU2425164C1 (en) 2010-01-20 2011-07-27 Открытое Акционерное Общество "Корпорация Всмпо-Ависма" Secondary titanium alloy and procedure for its fabrication
US10053758B2 (en) 2010-01-22 2018-08-21 Ati Properties Llc Production of high strength titanium
US9255316B2 (en) 2010-07-19 2016-02-09 Ati Properties, Inc. Processing of α+β titanium alloys
US8613818B2 (en) 2010-09-15 2013-12-24 Ati Properties, Inc. Processing routes for titanium and titanium alloys
US9206497B2 (en) 2010-09-15 2015-12-08 Ati Properties, Inc. Methods for processing titanium alloys
US10513755B2 (en) 2010-09-23 2019-12-24 Ati Properties Llc High strength alpha/beta titanium alloy fasteners and fastener stock
RU2463365C2 (en) * 2010-09-27 2012-10-10 Открытое Акционерное Общество "Корпорация Всмпо-Ависма" METHOD TO PRODUCE INGOT OF PSEUDO β-TITANIUM ALLOY, CONTAINING (4,0-6,0)%Al, (4,5-6,0)% Mo, (4,5-6,0)% V, (2,0-3,6)%Cr, (0,2-0,5)% Fe, (0,1-2,0)%Zr
US8652400B2 (en) 2011-06-01 2014-02-18 Ati Properties, Inc. Thermo-mechanical processing of nickel-base alloys
CN102586639A (en) * 2012-03-16 2012-07-18 广州有色金属研究院 Method for preparing titanium alloy through high-speed pressing formation
US9869003B2 (en) 2013-02-26 2018-01-16 Ati Properties Llc Methods for processing alloys
US9192981B2 (en) 2013-03-11 2015-11-24 Ati Properties, Inc. Thermomechanical processing of high strength non-magnetic corrosion resistant material
US9777361B2 (en) 2013-03-15 2017-10-03 Ati Properties Llc Thermomechanical processing of alpha-beta titanium alloys
US11111552B2 (en) 2013-11-12 2021-09-07 Ati Properties Llc Methods for processing metal alloys
JP6392179B2 (en) * 2014-09-04 2018-09-19 株式会社神戸製鋼所 Method for deoxidizing Ti-Al alloy
US10094003B2 (en) 2015-01-12 2018-10-09 Ati Properties Llc Titanium alloy
US10502252B2 (en) 2015-11-23 2019-12-10 Ati Properties Llc Processing of alpha-beta titanium alloys
CA3020443C (en) * 2016-04-25 2023-07-04 Arconic Inc. Bcc materials of titanium, aluminum, vanadium, and iron, and products made therefrom

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US2868640A (en) * 1955-01-11 1959-01-13 British Non Ferrous Metals Res Titanium alloys
US2893864A (en) * 1958-02-04 1959-07-07 Harris Geoffrey Thomas Titanium base alloys
US4134758A (en) * 1976-04-28 1979-01-16 Mitsubishi Jukogyo Kabushiki Kaisha Titanium alloy with high internal friction and method of heat-treating the same
US5332545A (en) * 1993-03-30 1994-07-26 Rmi Titanium Company Method of making low cost Ti-6A1-4V ballistic alloy
US5358686A (en) * 1993-02-17 1994-10-25 Parris Warren M Titanium alloy containing Al, V, Mo, Fe, and oxygen for plate applications
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US2754204A (en) * 1954-12-31 1956-07-10 Rem Cru Titanium Inc Titanium base alloys
US2868640A (en) * 1955-01-11 1959-01-13 British Non Ferrous Metals Res Titanium alloys
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US2893864A (en) * 1958-02-04 1959-07-07 Harris Geoffrey Thomas Titanium base alloys
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080199350A1 (en) * 2001-11-22 2008-08-21 Tetyukhin Vladislav Valentinov Metastable beta-titanium alloy
US9631261B2 (en) 2010-08-05 2017-04-25 Titanium Metals Corporation Low-cost alpha-beta titanium alloy with good ballistic and mechanical properties
US20160008903A1 (en) * 2014-07-10 2016-01-14 The Boeing Company Titanium Alloy for Fastener Applications
CN105316525A (en) * 2014-07-10 2016-02-10 波音公司 Titanium alloy for fastener applications
US9956629B2 (en) * 2014-07-10 2018-05-01 The Boeing Company Titanium alloy for fastener applications

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DE602005012284D1 (en) 2009-02-26
DK1783235T3 (en) 2009-03-16
EP1783235B1 (en) 2009-01-07
ES2320684T3 (en) 2009-05-27
RU2269584C1 (en) 2006-02-10
EP1783235A1 (en) 2007-05-09
ATE420217T1 (en) 2009-01-15
EP1783235A4 (en) 2008-02-13
WO2006014124A1 (en) 2006-02-09

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